N-phosphonomethyl amides

ABSTRACT

NEW COMPOUNDS ARE DISCLOSED OF THE FORMULA:   R-(-CO-NH-CH2-P(=O)(-OR&#39;&#39;)2)Y   WHEREIN R&#39;&#39; IS SELECTED FROM THE GROUP CONSISTING OF PHENYL, LOWER ALKENYL AND HALOGEN SUBSTITUTED AND UNSUBSTITUTED LOWER ALKYL OF 1-6 CARBON ATOMS, Y IS AN INTEGER FROM 1-2 PROVIDED THAT WHEN YS IS 1, R IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, LOWER ALKYL OF 2-8 CARBON ATOMS, BENZYL, DIALKYLPHOSPHONOALKYL AND PHENOXYMETHYLENE AND WHEN Y IS 2, R IS LOWER ALKYLENE OF 1-4 CARBON ATOMS. THE COMPOUNDS OF THE INVENTION ARE USEFUL AS FLAME RETARDANT AGENTS FOR TEXTILE MATERIALS AND IN THE PRODUCTION OF POLYMERS AND COPOLYMERS WHICH POSSESS FLAME RETARDANT PROPERTIES.

3,823,206 Ice Patented July 9, 1974 3,823,206 N-PHOSPHONOMETHYL AMIDESPeter Golborn, Lewiston, and James J. Duffy, Bulfalo, N.Y., assignors toHooker Chemical Corporation, Niagara Falls, N.Y. No Drawing. Filed Mar.30, 1972, Ser. No. 239,793

' Int. Cl. C07f 9/40; (308i 45/58 US. Cl. 260-932 13 Claims ABSTRACT OF.THE DISCLOSURE New compounds are disclosed of the formula:

t I RT NHCHziKO R02] wherein R' is selected from the group consisting ofphenyl, lower alkenyl and halogen substituted and unsubstituted loweralkyl of 1-6 carbon atoms, y is an integer from 1-2 provided that when yis 1, R is selected from the group consisting of hydrogen, lower alkylof 28 carbon atoms, benzyl, dialkylphosphonoalkyl and phenoxymethyleneand when y is 2, R is lower alkylene of 1-4 carbon atoms. The compoundsof the invention are useful as flame retardant agents for textilematerials and in the production of polymers and copolymers which possessflame retardant properties.

FIELD OF INVENTION This invention relates to novel compounds of theformula r 3 TNHCHaP (o R) :1

BACKGROUND OF THE INVENTION Many flame retarding agents and methods ofapplication have been developed in attempts to obtain flame resistanttextile materials and thermoplastic, thermosetting and elastomeric resincompositions.

Flame retardant textiles have been produced by depositing metal oxides,within or on the textile fibers, by the successive precipitation offerric oxides and a mixture of tungstic acid and stannic oxide or bysuccessive deposition of antimony trioxide and titaniumdioxide. Suchprocesses require plural treatment bathsin which strongly acidicsolutions are employedt'hus posing the problem of possible textiledegradation. Furthermore metal oxide coatings on textile materialscreate difliculties in subsequent dyeing processes which deleteriouslyafiect the hand of the finished product. Another process involves theuse of a single processing bath wherein a dispersion of a chlorinatedhydrocarbon andfinely divided antimony oxide is padded on the textilematerial. Near the textile combustion temperature antimony oxide willreact with hydrogen chloride, generated by degradation of thechlorinated hydrocarbon, to form antimony oxychloride which acts tosuppress flame. This combination of a chlorinated bydrocarbon and finelydivided antimony oxide are not acceptable finishes for closely woventextiles as they deleteriously afl ect the hand of the finished product.A further process for imparting flame resistance to cellulosic materialsis by the esterification of the cellulose with diammonium hydrogenorthophosphate. Textile products so treated however are subjected tometathesis reaction with cations during washing, and must be regeneratedby reacting the wash product with an ammonium chloride solution.

The production of thermoplastic, thermosetting and elastomeric resincompositions which are flame retardant is of considerable commercialimportance. For example, such articles as castings, moldings, foamed orlaminated structures and the like are required, or are at least desired,to be resistant to fire and flame and to possess the ability to endureheat without deterioration. The use of various materials incorporatedinto thermoplastic, thermosetting and elastomeric resins so as toimprove the flame retardancy thereof has been known. Many compounds havebeen commercially available for such use, among them being chlorostyrenecopolymers, chlorinated paraflin wax in admixture with triphenylstyrene, chlorinated paraflins and aliphatic antimonical compounds, aswell as antimony oxide-chlorinated hydrocarbon mixtures. A problemassociated with these compounds has been however, the fact thatgenerally a large amount, i.e. upwards of 35% of additive, must beincorporated into the resin in order to make it sutficiently flameretardant. Such large amounts of additive may deleteriously affect thephysical charac 'It is therefore, a principal object of this inventionto provide novel compounds of the formula:

wherein R is selected from the group consisting of phenyl, lower alkenyland halogen substituted-and unsubstituted lower alkyl of 16 carbonatoms, y is an integer from 1-2 provided that when y is l, R is selectedfrom the group consisting of hydrogen, lower alkyl of 28 carbon atoms,benzyl, dialkylphosphonoalkyl and phenoxymethylene and when y is 2, R islower alkylene of 1-4 carbon atoms.

It is also an object of this invention to provide flame retardingtextile materials comprising normally flammable cellulosic,proteinaceous or analogous man-made materials. Another object is toprovide a method for treat-' ing normally flammable cellulosic,proteinaceous or analogous man-made materials to render them flame re-,

tardant. Another object is to provide flame retarding thermoplastic,thermosetting or elastomeric resin composif" tions comprising normallyflammable resin materials. A

further object is to provide a process for treating 'no'rmally flammablethermoplastic, thermosetting or elastomeric;

resin compositions to render them flame retardant. A

particular object is to devise a composition comprising normallyflammable cellulosic, proteinaceous or analo gous man-made materials andan effective flame retardant amount of the compound represented by theformula wherein R, R and y are as above described.

A further particular object is to devise a composition comprisingnormally flammable thermoplastic, thermosetting or elastomeric polymerand an effective flame retarding amount of the before described novelcompound.

These and other objects of the present invention will be obvious fromthe following description.

DESCRIPTION OF THE INVENTION In accordance with this invention there areprovided novel compounds, for imparting flame retardancy to textiles andresin materials, of the formula wherein R' is selected from the groupconsisting of phenyl, lower allyl and halogen substituted andunsubstituted lower alkyl of 1-6 carbon atoms, y is an integer from 1-2provided that when y is 1, R is selected from the group consisting ofhydrogen, lower alkyl of 2-8 carbon atoms, benzyl, dialkylphosphonoalkyland phenoxymethylene and when y is 2, R is lower alkylene of 1-4 carbonatoms. More specifically, the preferred compounds of the presentinvention include these compounds wherein R' is lower alkyl of 1-6carbon atoms.

Illustrative examples of compounds of the present invention include, forinstance, compounds of the general formula such as H H HCNHCHzP CH5):

0 H CHjOHgCHzCNHCHPi (O CH3)2 I ll CECH2( ]NHCHzP(0CH1CHzCl)g II IICHaCHaOHzCHaCHzC-NHCHzP (O CHzCHBICHzBI):

4 The synthesis of the compositions of the present invention isaccomplished by reacting an N-hydroxymethyl amide of the formula RNHCHzOH with a trialkyl phosphite of the formula (R'O) P wherein R and Rare as previously described in a suitable solvent an excess of phosphiteor neat. Typically, the reaction occurs at elevated temperatures and iscontinued for about 1 to about 12 hours. Temperatures are generallyabout 50 C. to about 160 C. Preferably reaction is continued from about3 to about 6 hours at a temperature of about C. to about C. The solventor other volatile matter, is thereafter stripped, or otherwise removedfrom the product. Suitable solvents include benzene, toluene, xylene,glymes, dimethyl formamide, aliphatic or aromatic hydrocarbons. TypicalN-hydroxymethyl amides operable as reactants herein includeCHaCHgCHaCHzHlNHCHaOH O CH:CHz N-CH:OH

L-NH-CHaOH fi-NH-CHQOH ll C-NH-CHIOH One or more of the novel compoundsof this invention may be applied to textile materials by conventionalfinishing techniques such as by thermal induced pad curing so as toincorporate into the textile a flame retardant amount thereof. Thecompounds of this invention have advantages over the flame retardantagents of the prior art in that they may be used on a variety of textilematerials of different chemical composition, and they may be applied bya variety of methods. They may be applied to materials in either thefiber or fabric form to give flame retarding materials with minimumdetectable physical changes in the quality or hand of the textilematerial.

Products of this invention may be applied to cellulosic material inseveral ways to givea durable flame retardant treatment. For example,the products of this invention may be reacted with formaldehyde to giveN-hydroxymethyl derivatives which can react with cellulosic materials ina known manner. Alternatively aqueous mixtures of the products withformaldehyde, urea, trimethylol melamine or other known cellulosecrosslinking agents may be applied to cellulose substrate with the aidof an, acidic catalyst by a padding process.

More preferably the N-hydroxymethyl derivative of the products of thisinvention prepared by the condensation of the products withformaldehyde, are mixed in an aqueous medium with trimethylol melamineand a Lewis acid cata lyst such as NH Cl or Zn(NO -6H O. The cellulosicmaterial is immersed in an aqueous solution of the methylol derivative,trimethylol melamine, and

and squeezed on a two roll padder to 70-90% wet weight pick-up. Thematerial is dried at 220-270 F. for 1-3 minutes and cured at 300370 F.for 1-6 minutes in a circulating air oven. The samples are then washedin hot water and dried. The finished samples have a flame retardantadd-on of about to about 40% and preferably about to about 25% byweight.

The flame retardant agents of this invention may be applied to varioustextiles such as cellulosic materials, proteinaceous materials andblends of cellulosic or proteinaceous materials with analagous manmadefibers. By cellulosic materials, applicant intends to embrace cotton,rayon, paper, regenerated cellulose and cellulose derivatives whichretain a cellulose backbone of at least one hydroxy substituent perrepeating glucose unit. By proteinaceous material applicant intends toembrace those textile materials comprising the functional groups ofproteins such as the various animal wools, hairs and furs.

The flame retardant compounds or additives of the invention may beincorporated into resin compositions by any known method. That is tosay, the flame retardant additive may be added to the resin by millingthe resin and the additive on, for example, a two-roll mill, or in aBanbury mixer etc., or it may be added by molding or extruding theadditive and resin simultaneously, or by merely blending it with theresin in powder form and thereafter forming the desired article.Additionally, the flame-retardant may be added during the resinmanufacture, i.e., during the polymerization procedure by which theresin is made, provided the catalysts etc. and other ingredients of thepolymerization system are inert thereto. Generally, the compounds ofthis invention may be incorporated into the thermoplastic resin inflame-retarding amounts, i.e. generally amounts ranging from about 5% byweight, to about 50% by weight, preferably from about 20% by weight, toabout 40% by weight, based on the weight of the polymer, have been foundsufficient.

Resins embraced within the scope of this invention include thehomopolymers and copolymers of unsaturated aliphatic, alicyclic, andaromatic hydrocarbons. Suitable monomers are ethylene, propylene,butene, pentene, hexene, heptene, octene, 2-methylpropene-1,3-methylbutene- 1, 4-methylpentene-1, 4-methylhexene-1, 5-methylhexene-1, bicycle-(2.2.1)-2-heptene, butadiene, pentadiene, hexa- 6 diene,isoprene, 2,3-dimethylbutadiene-l,3, 2-methylpentadiene-1,3,4-vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene andmethylstyrene, and the like.

Other polymers in addition to the above-described olefin polymers thatare useful in the invention include polyindene, indenecoumarone resins;polymers of acrylate esters and polymers of methacrylate esters,acrylate and methacrylate resins such as ethyl acrylate, n-butylmethacrylate, isobutyl methacrylate, ethyl methacrylate and methylmethacrylate; alkyd resins and paint vehicles, such as bodied linseedoil; cellulose derivatives such as cellulose acetate, cellulose acetatebutyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose,methyl celluose and sodium carboxymethy cellulose; epoxy resins; furanresins (furfuryl alcohol or furfural-ketone); hydrocarbon resins frompetroleum; isobutylene resins (polyisobutylene); isocyanate resins(polyurethanes); melamine resins such as melamine-formaldehyde andmelamine-urea-formaldchyde; oleo-resins; phenolic resins such asphenolformaldehyde, phenolic-elastomer, phenolic-epoxy,phenolic-polyamide, and phenolic-vinyl acetals; polyamide polymers, suchas polyamides, polyamide-epoxy and particularly long chain syntheticpolymeric amides containing recurring carbonamide groups as an integralpart of the main polymer chain; polyester resins such as unsaturatedpolyesters of dibasic acids and dihydroxy compounds, and polyesterelastomer and resorcinol resins such as resorcinol-formaldehyde,resorcinol-furfural, resorcinol-phenolformaldehyde, resorcinol-polyamideand resorcinol-urea; rubbers such as natural rubber, syntheticpolyisoprene, reclaimed rubber, chlorinated rubber, polybutadiene,cyclized rubber, butadiene-acrylonitrile rubber, butadienestyrenerubber, and butyl rubber; neoprene rubber (polychloroprene);polysulfides (Thiokol); terpene resins; urea resins; vinyl resins suchas polymers of vinyl acetal, vinyl acetate or vinyl alcohol-acetatecopolymer, vinyl alcohol, vinyl chloride, vinyl butyral, vinylchloride-acetate copoly mer, vinyl pyrrolidone and vinylidene chloidecopolymers; polyformaldehyde; polyphenylene oxide; polymers of diallylphthalates and phthalates; polycarbonates of phosgene or thiophosgeneand dihydroxy compounds such as bisphenols, phosgene, thermoplasticpolymers of bisphenols and epichlorohydrin (trade named Phenoxypolymers); graft copolymers and polymers of unsaturated hydrocarbons andunsaturated monomer, such as graft copolymers of polybutadiene, styreneand acrylonitrile, commonly called ABS resins; ABS polyvinyl chloridepolymers, recently introduced under the trade name of Cycovin; andacrylic polyvinyl chloride polymers, known by the trade name Kydex 100.

The polymers of the invention can be in various physical forms, such asshaped articles, for example, moldings, sheets, rods, and the like;fibers, coatings, films and fabrics, and the like.

The compounds of this invention have been found to have particularutility in ABS resins and in elastomeric materials such as acrylicrubber; acrylonitrile-butadiene styrene terpolymers;butadiene-acryloniuile copolymers; butyl rubber; chlorinated rubbers,e.'g., polyvinyl chloride resins, chloroprene rubber, chlorosulfonatedpolyethylene; ethylene polymers, e.g., ethylene-propylene copolymers,ethylene-propylene terpolymers; fluorinated rubbers, butadiene rubbers,e.g., styrene-butadiene rubber, isobutylene polymers, polybutadienepolymers, polyisobutaylene rubbers, polyisoprene rubbers; polysulfiderubbers; silicon rubbers; urethane rubbers; high styrene resins latices,high styrene resins, vinyl resins; sponge rubber; and the like.

It should be noted that it is also within the scope of the presentinvention to incorporate such ingredients as plasticizers, dyes,pigments, stabilizers, antioxidants, antistatic agents and the like tothe novel composition.

ASTM Test D2863-70, used in accordance with the following examples,generally provides for the comparison of relative flammability ofself-supporting plastics by measuring the minimum concentration ofoxygen in a slowly rising mixture of oxygen and nitrogen that willsupport combustion. The procedure encompasses support ing cylindricaltest specimens 70-150 x 8.0mm. vertically in a glass tube fitted withcontrolled upward oxygen-nitrogen gas flow. The top of the specimen isignited and oxygen flow is adjusted until it reaches that minimum rateat which the specimen is extinguished before burning 3 minutes or 50 mm.Whichever happens first. The oxygen index(n) is then calculated asfollows:

n, percent: (100x0 (Oz-I-Nz) wherein O is the volumetric flow of oxygen,at the minimal rate and N is the corresponding volumetric flow rate ofnitrogen.

A modification of ASTM Test D635-68 used in accordance with thefollowing examples, generally provides for the comparison of burningrates, self-extinguishment and non-burning characteristics of plasticsin the form of sheets, bars, plates or panels. The procedure encompassespreparing cylindrical plastic samples of 150-200 mm. x 8 mm. diameterwith and without the subject flame retardant additive. Each sample ismarked at points 1 inch and 4 inches from its end and held, marked endin the flame, at a 45 degree angle in a controlled burner flame (1 inchflame length) for two 30 second attempts. The movement of the flame upthe length of the sample through the two points is measured for rate ofburning, non-burning or self-extinguishing characteristics. A sample israted SE (self-extinguishing) if the flame burns through the first pointbut extinguishes before reaching the second point. A sample is rated NB(non-burning) if, upon ignition it does not burn to the first point.

AATCC test method 34-1969, The Vertical Char Test, used in accordancewith the following examples, generally provides for the comparison ofrelative flammability of 2% inch x 10 inch fabric test specimens whenexposed to a controlled burner flame, under controlled conditions, forperiods of 12.0 and 3.0 seconds. Charred specimens are thereaftersubjected to controlled tearing tests, using tabulated weights, todetermine the average tear length as representing the char length of thefabric. In addition, samples which are wholly consumed by the flame arerated (B) and sample which do not burn are rated (NB). For comparisonpurposes, it should be noted that untreated samples of the fabrics usedin the examples of this case would be consumed for this test.

In all the examples of the application, the following general procedurewas used except when otherwise specifically noted. Padding was done on astandard two roll laboratory padder at a gauge pressure of about 60pounds per square inch in all cases. Drying and curing during processingwere done with a standard laboratory textile circulating air oven.Washing and drying was done in a standard, home, top loading, automaticwasher and dryer. A Hooker Boil (HB) is done in a standard, center post,wringer washer fitted with internal steam coils. The sample to betreated is Washed and agitated therein for 45 minutes in a solutioncontaining 88 pounds of water, 100 grams of sodium carbonate, 100 gramsof Ivory soap and 10 grams of Tide detergent at a temperature of about200 to about 210 Fahrenheit. The washer is then drained, the samplesqueezed through the wringer and again washed and agitated therein forminutes in about '88 pounds of water at about 140 to about 160Fahrenheit.

The following examples are set forth for purposes of illustration onlyand are not to be construed as limitations of the present inventionexcept as set forth in the appended claims. All parts and percentagesare by Weight unless otherwise specified.

EXAMPLE I Preparation of l? n HGNHCHzP(OOHa)2 N-hydroxymethyl formamide(0.5 mole) was mixed with trimethylphosphite (0.5 mole) in a roundbottomed, three necked flask fitted with a thermometer, reflux condenserwith take off and a magnetic stirrer. The mixture was heated slowly toabout 100 C. and distillate collected for about two hours. Thedistillate was identified by infrared analysis as methanol. After thedistillate ceased the reaction mixture was heated to about 120 C. andheld at that temperature for about one half hour. The mixture was thenstripped on a rotary evaporator at about C. and 5 mm. Hg, for about onehour to remove all volatiles. The resulting product was identified asN-dimethylphosphonomethyl formamide and was obtained in 98% yield.

EXAMPLE II Preparation of H H CHaCHzCHzONI-ICHzP (0 CH3):

In a 500 ml. round bottomed flask was placed 81.9 g. (0.70 mole) ofN-hydroxymethylbutylamide and 124 g. (1.0 mole) of trimethyl phosphite.The mixture was heated to reflux and held at that temperature for aboutsix hours. The reaction was then cooled, stripped, at 1990 C. and 2 mm.Hg pressure, to remove any volatiles. Infrared and nuclear magneticresonance spectroscopy identified the product as essentially pureN-dimethylphosphonomethylbutylamide in 76.7% yield.

EXAMPLE III A flask, fitted with reflux condenser, stirrer andthermometer, was charged with 88 g. (0.5 mole) N,N'-bis hydroxymethylsuccinamide and 186 g. (1.5 mole) trimethyl phosphite and was refluxedat about 92 for about 4 hours. mls. of toluene was added to the reactionand reflux was continued for 25 hours. The reaction mixture was cooledand solidified by addition of 500 mls. acetone. The reaction mixture wasthen filtered to give 12 g. solid (M.P. 236245). Infrared spectra andelemental analysis indicated the solid was succinamide.

The filtrate was then stripped, under 10 mm. Hg vacuum at 70 C. to give182 g. of amber liquid. This liquid was further distilled under vacuumto remove excess trimethyl phosphite. After distillation 144 g. of amberliquid remained.

The structure was confirmed by elemental analysis and infrared andnuclear magnetic resonance spectroscopy to beN,N-bis(dimethylphosphonomethyl) succinamide.

EXAMPLE IV A 1 liter flask was fitted with reflux condenser, stirringand thermometer. The flask was charged with 430 g. 1.86 mole) ofN-hydroxymethyl diethylphosponoacetamide and 248 g. (2.0 mole) oftrimethyl phosphite. The reaction mixture was heated for about 13 hoursat about C. Excess trimethyl phosphite was removed by vacuumdistillation to give 528.5 g. of a thick yellow liquid.

The product structure was confirmed by elemental analysis and infraredand nuclear magnetic resonance spectroscopy todiethylphosphonoacetamide.

EXAMPLE V Preparation of 0 llv H (CHaOMPCHzCHzNHCHzP (0 CH3):

Trimethyl phosphite (2.0 mole) was mixed with N- hydroxymethyl 3dimethylphosphonopropionamide (1.0 mole) in a one liter flask, fittedwith thermometer, mechanical stirrer, distillate take off, and refluxcondenser, and heated to reflux for about 2 hours. A mixture of methanoland trimethyl phosphite was removed as distillate and an equivalentvolume of trimethyl phosphite added during the second hour of reflux.

After the heating period, when no more methanol was evident in thedistillate, the excess phosphite was removed under reduced pressure. Theproduct, a clear viscous oil, was obtained in 95% yield and was thestructure N-dimethylphosphonomethyl 3 dimethyl phosphonopropionamidewhich was confirmed by elemental analysis and infrared spectroscopy.

EXAMPLE VI Preparation of A 500 ml. round bottomed flask was chargedwith 124 g. (1.0 mole) of trimethyl phosphite and heated to 100 C. Tothis was added 132 g. (0.8 mole) of N-hydroxymethylphenylacetamide overa ten minute period of time. The mixture was held at about 96 for aboutsix hours, cooled, filtered, and stripped, at 100 C. and 0.25 mm. Hg, togive a 64% yield of the desired product in the form of a pale yellowoil. Elemental analysis as well as infrared and nuclear magneticresonance spectroscopy confirmed the structure.

EXAMPLE VII Preparation of Trimethyl phosphite (62 g. 0.5 mole) washeated to about 100 C. in a round bottom flask.N-hydroxymethylphenoxyacetamide (54 g., 0.3 mole) was added over a 5.0minute time period and the mixture heated at about 92 for about twohours. After the heating period the mixture was stripped, at 100 C. and0.5 mm. pressure, to give 90% of the desired product.

EXAMPLE VIII Preparation of N-hydroxymethyl phenyl acetamide (14.0 g.0.085 mole) was heated with triphenyl phosphite (27 g. 0.085 mole) at120-124" C. for about five hours in a round bottomed flask. The reactionmixture was then stripped, at 120 C. and 2 mm. pressure, to removephenol and other volatile material to give the desired product (29.4 g).The product was confirmed by infrared and nuclear magnetic resonancespectroscopy.

. EXAMPLE IX Preparation of In a 250 ml. round bottomed flask 17.6 g. ofN,N bis hydroxymethyl succinamide and 62 g. of triphenyl phosphite wereheated at about 130 C. for about five hours. Upon completion of theheating the reaction mixture was stripped, at 120 C. and 2 mm. Hg, toremove phenol and other volatile material. The product was a thickyellow semi solid and was obtained in 89.3% yield. The structure of thedesired product was confirmed by spectroscopic and elemental analyses.

EXAMPLE X Preparation of N-diphenyl phosphonomethyl propionamide, wasprepared in 82.2% yield by heating N-hydroxymethylpropionamide (0.2mole) and triphenyl phosphite (0.2 mole) at about 130 for about 5 hours.After the heating period was completc'phenol Was removed under reducedpressure (2 mm. Hg) at 120. The product structure was 10 confirmed byinfrared and nuclear magnetic resonance spectroscopy.

EXAMPLE XI Preparation of CHzCHrCHgEiNHCHziKOCH2CH=CH2)2 Triallylphosphite (40.2 g. 0.2 mole) was mixed with N-hydroxymethyl butyramide(23.4 g. 0.2 mole) in a round bottomed flask and heated about four hoursat about C. At the end of this time the reaction mixture was stripped atabout 125 C. and 2 mm. pressure. The product obtained was a red-brownliquid and its structure was confirmed by elemental analysis andinfrared and nuclear magnetic resonance spectroscopy.

EXAMPLE XII Preparation of 0 ("I-NH-CHz-P (O CHzCHzCDg (C Hz) 2 OfiJ-NH-CHr-i' (0 0112011101): 0

A mixture of tris-Z-chloroethyl phosphite (0.2 mole) andN,N'-bis-hydroxymethyl succinamide (0.1 mole) was heated in a roundbottomed flask at about C. for about 6 hours. The reaction mixture wasthen stripped, at 100 C. and 2 mm. Hg pressure, to remove any volatilematerial. 43 grams of N,N'-bis-(2-chloroethyl)phosphonomethylsuccinamide was obtained as a brown wax.

EXAMPLE XIII Thirty parts of N-dimethylphosphonomethyl butylamide andseventy parts of polystyrene were dry blended for about 5 minutes. Thismixture was then brought to a melt and mixed thoroughly for about 15minutes, cooled, and chopped into small pieces. These pieces were thenmolded into a solid cylinder 200 mm. x 8 mm. and tested by ASTM testsD2863-70 and D635-68 as described above. Results of these tests arecontained in Table I.

EXAMPLESS XIV-XXVI Using the procedure of Example 13, various plasticcompositions were prepared and tested containing various flameretardants. The results are set forth in Table I.

EXAMPLE XXV II 5.0 02. cotton sheeting was padded through a solutioncontaining 30 parts ofN-dimethylphosphonomethyl-3-dimethylphosphonopropionamide, 10 parts oftrimethylolmelamine, 30 parts of 40% formalin solution, 25 parts ofwater and 5 parts of Zn(NO .6H O.

The sheeting was squeezed to a 80% wet pick-up by means of a two rolllaboratory padder, and thereafter dried at about 250 F. for about twominutes and cured at about 340 for about 4 minutes in a circulating airoven. The sheeting was then washed for one wash cycle, in a standardhome type automatic Washer with Tide detergent and tumble dried. A resinadd-on of 24.7% was obtained. The sheeting was then subjected to AATCCtest method 34-1969 and had a calculated char length of 4.5 inches. Thesheeting was then subjected to one hooker boil and when tested by AATTCtest method 34-4969 had a calculated char length of 5.5 inches.

EXAMPLE XXVIII 8.0 oz. per sq. yd. wool Bedford cord was padded throughthe solution of Example XXVII and squeezed to 60% wet pick-up. Afterdrying curing and washing as in Example XXVII a Resin add-on of 17.7%was obtained. Initial testing under AATCC test method 34-1969 indicatesa 1.5 inch calculated char length. The wool Bedford cord was thensubjected to 24 additional washes in a standard home type automaticwasher using Tide de- 1 1 tergent and tumble dried. Testing by method34-1969 indicated a calculated char length of 3.0 inches.

EXAMPLE XXIX A rayon staple fiber sample was immersed in the solution ofExample XXVII and squeezed to 100% Weight gain. The sample was dried forminutes at 240 F. and cured minutes at 340 F., washed in hot tap water,and dried to give a 32% add-on.

A treated sample is self-extinguishing if ignited in a Bunsen flame andthen removed while an untreated sample is completely consumed.

The treated sample remains self-extinguishing after 10 home washes in anautomatic washer.

EXAMPLE XXX A solution of N-dimethylphosphonomethylphenyl acetamide (0.2mole) and 38% formalin solution (0.2 mole) in 50 g. of water wasrefluxed about one hour at a pH of 9 and then stirred an additional 3hours at room temperature. The pH was adjusted to 7.0 and 20 g. oftrimethylolmelamine and 5 g. of magnesium chloride hexahydrate added.5.0 oz. cotton sheeting was padded through the solution and squeezed toa wet pick-up of 120% on a two roll laboratory padder. The sheeting wasthen dried at about 240 F. for about 2 minutes and cured at about 350 F.for about 3 minutes in a circulating air oven. The sheeting was thenWashed by hand for about 5 minutes using Tide detergent. Testing underAATCC method 24-1969 gave a 2.0 inch calculated char length. Aftersubjected to a second hand washing as above described, testing gave a1.9 inch calculated char length.

EXAMPLE XXXI N,N'-bis-dimethylphosphonomethyl succinamide (40 g.) wasmixed with 40% formalin solution (60 g.) and stirred overnight at a pHof 10. The pH was then adjusted to 7.0 with hydrochloric acid and 23 g.of a 50% solution of a methylolated malamine and 5 g. of ammoniumchloride added.

6.0 oz. sq. yd. wool sample was padded through the solution and squeezedto about 130% wet pick-up on a two roll laboratory padder at 60' lb.gauge pressure. The

treated wool was then dried at about 250 F. for about 2 minutes andcured at about 350 F. for about 4 minutes in a circulating air oven. Thetreated wool was then Washed by hand for about five minutes using Tidedetergent and tumble dried. A resin add-on of 41% and oxygen index of 28was calculated. The thus treated wool was then subjected to AATCC method34-1969- and found to have a calculated char length of 3.0 inches. Thetreated wool was then subjected to 4 additional hand Washes, on abovedescribed, and after testing by method 34-196-9 had a char length of 4.0inches.

EXAMPLE XXXII A padding solution was prepared as in Example XXXI usingN-dimethylphosphonomethylbutyramide as the phosphorus containingspecies.

6 oz. per sq. yd. wool was treated by the process of Example XXXI usingthe above described padding solution. Resin add-on was calculated to be30% and oxygen index 28. Testing under method 34-1969 after one washgave a calculated char length of 3.6 inches and after 4 additionalwashings, a calculated char length of 4.0 inches.

EXAMPLE XXXIH N-dimethylphosphonomethylformamide (40 g.) was mixed with40% formalin solution g.) and stirred overnight at pH 9-10. The pH wasadjusted to 7.0 with hydrochloric acid and then 23 g. of a 50% solutionof a methylolated melamine and 5 g. of ammonium chloride were added.

A rayon staple fiber was immersed in the above solution and squeezed toabout wet pick-up on a two roll laboratory padder. The fiber was thendried in a circulating air oven for about five minutes at about 250 andcured about ten minutes at about 350, washed in hot water by hand, andair dried giving about 32% resin add-on.

The oxygen index of the fiber was calculated as 29.5 as compared to 19.5for untreated fiber. The treated samples self-extinguished when a Bunsenflame was applied for 2 seconds and removed while untreated samplesburned completely. The self-extinguishing character is maintained after5 hot water, hand washings.

TABLE I Percent 1 53%;

Example Polymer Compound mixtu rg OI D-635 XIII Polystyrene 30 SECHa(CH2)2 NHGHzi (OCH3)z XV...'.-.."..'.-.- Epoxy H H (0 35 25 SECHaCHgCNHCHgP- XVI....--.-.:;:. Polyethylene terephthalate O 30 25.5 NB

HiilNHGHzPQCHa):

xx an 40 20.5

410 CHN J NHCHA Q CH3):

YXT ABS. 40 20 TABLE I-Continued Percent compound Example PolymerCompound mixtu r OI D-635 YYTT ABS H 40 24 6 n n (CH30)2PCH:NHGOHzCH2CNHCHz] (O CHa):

XXIII Nylon 40 25 n n u (CH 0)P CH2NHCCHr-CHa-CNHCHzi"(O CH3):

XXIV Polyethylene terephthalate... H H 40 34 NB II I (CH30)2PCH2NHCCH2CHzC-NHOHz1 (0 CH3):

XXV SBR H H H H 30 20.2 SE

(CH30)2P CHzNHC-C Hfl-C H2G-NHCH2P(O CH3):

XXVI Polypropylene H u (I? H 30 23. 5 SE (ClCHzCHzOhP CHzNHCCH2CH2CNHCHBP(O CH2CH2C1):

We claim: 8. A compound of Claim 1 of the formula 1. A compound of theformula wherein R is selected from the group consisting of phenyl,

lower alkenyl and halogen substituted and unsubstituted consisting ofhydrogen, lower alkyl of 2-8 carbon atoms,

benzyl, lower dialkylphosphonoalkyl and phenoxymethylene and when y is2, R is lower alkylene of 1-4 carbon 9. A compound of Claim 1 of theformula 10. A compound of Claim 1 of the formula atoms.

2. A compound of Claim 1 of the formula (i: H CH:CHZ%NHOHZIIL(O)2 H N2P(OCHa)2 12. A compound of Claim 1 of the formula 3. A compound of theformula of Claim 1 E u omcmcmcmuomiwo0H10H=oHm CHQCHICHZ NHCH1P(OGH:)213. A compound of Claim 1 of the formula 4. A compound of Claim 1 of theformula 0 H J H -NH0Hz-%(0CHCH0D (cH=0)zP CHqHNCOHz-CHz-JE-NHCHrPWCHa):0 5. A compound of Claim 1 of the formula C NH CH 1 (OOH OH On(cmcmonrCH1E-NHCH1P(OCHQ)Z f ct d 6. A compound of Claim 1 of theformula 5 Re erences l e 0 UNITED STATES PATENTS ll OH2CHNHCH2,(OCHQI3,579,532 5/1971 Nadbur et a1 260-932 X 7. A compound of Claim 1 of theformula ANTON H. SUTTO, Primary Examiner US. Cl. X.R.

-' P0405 I "UNITED STATES PATENT OFFICE- CERTIFICATE OF CORRECTIONPatent No. 3,823,206 Dated I July 9 1974 lnventofls) "*Pieter Golborn etal. I

It is certified that error appears in the above-ideutified' patent V andthat said Letters Patent are hereby corrected as shown below:

Column 14, lines 44-46, (Claim 13) the formula reading v o 0 u I n v CNH- CH P(OCH CH Cl) II C- -NH-CI-I P(OCH CH C1) II I I Signed and sealedthis 31st day .of December 197 (SEAL) Att-est:

McC OY My GIBSON JR. 7 C. IIARSHALL DANN Arresting, Officer Commissionerof Patents

